Process for dyeing and printing



Patented Aug. 7, 1934 UNITED STATES PATENT OFFICE PROCESS FOR DYEING AND PRINTING TEXTILE MATERIAL Miles Augustinus Dahlen, Wilmington,

and

Frithjof Zwilgmeyer, Gordon Heightu. Del.I aasiqnors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation Delaware No Drawing. Application December 8, 1932,

. Serial No. 645,585

16 Claims.

ing with compositions comprising an ice color 6 coupling component and a diazoimino compound which is produced by coupling a secondary sugar amine with a diazotized aromatic amine containing no water solubilizing group.

It is an object of this invention to produce 10 dyeings and printings of excellent fastness on textile material. A further object is to produce results which are superior to those obtained with the tedious dyeing and printing processes previously used, by a much simpler method. Addil tional objects will appear hereinafter.

These objects are attained by the present invention wherein the material to be dyed or printed is treated with a mixture comprising anice color coupling component and a diazoimino compound which is produced by coupling a secondary sugar amine with a, diazotized aromatic amine containing no water solubilizing group. This diazoimino compound has the following general formula:

Aryl" represents an aromatic radical" (Ci. M)

azotized meta-chloroaniline, of the tollowinz probable structure:

one

omouomiomon was mixed mechanically with 5.03 parts of the ortho-toluidide of 2:3-hydroxy-naphthoic-acid. To this mixture was added with stirring 3.00 parts of Turkey red oil, followed by 5.70 parts of a 30 per cent solution of sodium hydroxide. 18.77 parts of water heated to 160 F. was neat added; and when a clear solution was obtained, 60.00 parts of a neutral starch-gum tragacanth thickener was added. The whole was agitated to a smooth printing paste.

Cotton piece goods were printed from an engraved copper roll with the above paste. The printed fabric was dried in the air, then steamed.

A developing bath of the following composition was prepared and heated to 205 F.:

Pam; Glacial acetic acid 1.0 Formic acid 0.5 Giaubers sa 2.5 Water 96.0

- 100.0 The printed and aged fabric was immersed in the bath for about 20 seconds, holding the temperature at 205 F., resulting in the development according to the printed pattern of the dyestufl of the following probable formula:

The invention will be more completely understood by reference to the following illustrative 40 examples in which the quantities are stated in parts by weight.

Example I 7.5 parts of the dry diazoimino compound prepared by the action of methyl-glucamine on di- When color development was complete, the printed fabric was rinsed, soaped with a hot soap solution, again rinsed and dried.

The pattern was developed to a beautiful orange shade, showing excellent fastness to washing, light, and so forth.

Example II A printing paste of the following composition was prepared as in Example No. I.

7.0 parts of the diazoimino compound obtained by the action of diazotized metachloroaniline on methyl-galactamine, of the probable formula:

2.85 parts of the ortho-toluidide of 2:3-hydroxy-naphthoic-acid 3.00 parts of sodium hydroxide solution of 30 per cent strength 87.15 parts of neutral thickener The fabric was printed and steamed according to the method described in the previous example, and the dyestuif developed by the same procedure. The color formed on the fiber was chemically identical with that obtained according to Example No. I, and the printed pattern was again developed as a beautiful orange of excellent fastness properties.

Example III A printing paste of the following composition was prepared:

5.4 parts of the diazoimino compound ob- Cotton piece goods were printed with the above paste, from an engraved copper roll, the printed material dried and then subjected to the action of live steam containing acetic acid vapors. When color development was complete, the printed fabric was washed with water, treated with a hot soap solution, rinsed and dried. The pattern was developed as a bright red dyeing of excellent fastness properties, the color being due to the development on the fiber of the dyestuif of the probable formula:

i c ONHQ Example IV The process of Example No. III was repeated,

using a paste of the following composition:

2.7 parts of the reaction product of diazotized 4-chloro-2-amino-anisole and butylglucamine, of the probable formula:

OCH:

10.0 parts of ethyl alcohol 14.8 parts of water 2.96 parts of the ortho-anisidide of 2:3-hydroxy-naphthoic-acid 3.00 parts of caustic soda solution of 30 per cent strength 66.54 parts of neutral thickener The pattern was developed to a bright red, due to the formation of the dyestufi of the formula given in the previous example.

Example V A printing paste was prepared of the following composition:

2.7 parts of the diazoimino compound obtained by the action of butyl-xylamine on diazotized 4-chloro-2-amino-anisole, of the following probable formula:

10.0 parts of 23 alcohol 14.8 parts of water 2.96 parts of the ortho-anisidide of 2:3-hydroxy-naphthoic-acid 3.00 parts of sodium hydroxide solution of 30 per cent strength 66.54 parts of neutral thickener The printed fabric was developed without steaming in a bath prepared from:

Parts Acetic acid 100% 1.0 Formic acid 85% 0.5 Sodium sulfate 2.5 Water 96.0

the bath being previously heated to 205 F. and held at this temperature during the color development. When the dyestufl? was completely formed on the fiber, the cloth was washed, soaped, rinsed 0 and dried. The pattern was developed as a bright red of good iastness properties. The dyestufi was identical with that obtained in the previous example.

Example VI A printing paste was prepared from:

3.92 parts of the reaction product oif diazotized para-chloro-ortho-toluidine and methyl-glucamine, of the probable formula:

CHI

4.28 partsof the ortho-phenetidide of 2:3 hy-' droxy-naphthoic-acid 3.00 parts oi Turkey red oil '7 .00 parts of caustic soda of 30 per cent strength 14.80 parts of water heated to 160 F. 67.00 parts of starcht-tragacanth thickener The cotton piece goods were printed as in the previous example and the dyestufl developed on the fiber by treatment in the acetic-acid-formicacid-sodium-sulfate bath at 200-210 F. The pattern was developed as a bright scarlet dyeing of excellent fastness properties, the color being due tie the formation of the dyestufi oi the probable formula:

Example VII Equal quantities of the diazoimino compound from diazotized 4-chlorc=-2-toluidine and methylglucamine, of the formula given in the previous example, and the sodium salt of the orthophenetidide of 2:3-hydroxy-naphthoic-acid were intimately mixed. A printing paste of the following composition was then prepared:

Parts Mixture of diazoimino compound and orthophenetidide of 2:3-hydroxynaphthoic-== arid 8.6 Water 23.2 Turkey red o 3.0 Caustic soda of 30 per cent strength 3.2 Neutral thickener 62.0

Cottongoods were printed and developed as in the previous example, the same excellent scarlet dyeing being obtained.

Example VIII Cotton piece goods were printed with the above paste, from an engraved roll. The printed fabric was then subjected to the action of saturated steam containing the vapors of acetic acid, at a temperature of about 212 F. Rapid development of the pattern to a bright red was effected. When the formation of color was complete, the fabric was rinsed, soaped at the boil, rinsed and dried. The fast red printing had resulted from the formation 0! the "ice-color of the probable formula:

on; v

- 1 I ONHQ V Ha Example UK The process of Example No. VIII was repeated,

using a paste of the following compositiom.

2.7 parts of the diazoiminc compound obtained by the action of diazotized 4- chloro -'2 amino toluene on methyh xylamine, of the probable formula:

10.0 parts of ethyl alcohol 14.8 parts of water 2.96 parts of the ortho-toluidide of 213-113;- droxy-naphthoic-acid 3.00 parts of sodium hydroxide of 30 per cent strength 66.54; parts of neutral thickener As in the previous example, the pattern was developed as a beautii'ulred dyeing of excellent fastness properties. The dyestuif of the formula. given in that example is also formed in this case.

Example X Well-boiled and dried cotton yarn was im pregnated with the anilide oi 2:3-hydroxynaphthoic-acid wrung as dry as possible, and immediately developed in the following bath:

5. parts or the diazoimino compound obtained by the action of diazotized meta-chloroaniline on ethyl-glucamine, of the probable formula:

i. 0 part of glacial acetic acid 0. part of formic acid 2. 5 parts of Glauber's salt 91. 0 parts of water After color development was complete, the yarn was rinsed, soaped at the boil, rinsed and dried. The fastness of the dyeing thus obtained is excellent.

Example XI Cotton piece goods were impregnated with the ortho-toluidide of 2:3-hydroxy-naphthoic-acid in the usual manner. It was dried, then printed from an engraved roll with a paste of the following composition:

8parts of the diazoimino compound obtained by the action of methyl-glucamine on diazotized meta-chloro-aniline, of the formula given in Example No. I 3 parts of Turkey red oil 1 part of caustic soda of per cent strength 23 parts of water parts of starch-gum tragacanth thickener The printed fabric was steamed, then developed by the method described in Example No. I. The

printed material was washed in the usual manmatic amines commonly used in the ice color art, among which are the following:

3-nitro-4-amino-toluene, 2:5-dichloroaniline, 4-chloro-2-amino-toluene, 4-chloro-2-amino-anisol, ortho-chloro-aniline, meta-chloro-anlline. para-nitraniline, 1 -amino-4-benzoylamino-2 5- diethoxy-benzene, 4-chloro-2-nitro-aniline, N- (para amino benzoyl) -aniline, ortho phenetidine-azo-a.lpha-naphthylamine, para-anisidineazo-2 S-dimethoxy-aniline, alpha amino an thraquinone, 3-amino-carbazole, dianisldine, para-amino-diphenyl, 4,4'-diamino-diphenylamine, 1-amino-2-methoxy-naphthalene.

Methyl-glucamine, ethyl-glucamine, cyclohexyl-glucamine, benzyl-xylamine, methylerythramine, ethyl galactamine, amyl-arabinamine, methyl-mannamine.

Preparation of the secondary sugar amines may be carried out by any of the usual processes. For example, the liquid phase catalytic hydrogenation of a mixture of an aldose of the following general formula:

CHO-(CHOH) :CHzOH in which a: represents one of the integers 2, 3, 4; and a primary amine having the general formula:

in which R represents an alkyl, aralkyl, or completely reduced carbocyclic group. The different optical modifications of the aldoses, namely, the dextro-, laevo-, meso-, and racemic modifications may be used in preparing this secondary sugar amine.

The diazoimino compound may then be mixed with one of the usual ice color coupling components. such as an arylamide 0f 2-3-hydroxynaphthoic acid, an arylamide of hydroxy-carbazoleor hydroxy-naphthocarbazole-carboxylic acid, an arylamide of hydroxy-anthracene-carboxylic acid, alphaor beta-naphthol, an acetoacetyl derivative of an arylamine, or phenylmethyl pyrazolone. It is to be understood that this mixture may contain one or more diazoimino compounds and. one or more ice color coupling components, since certain shades are obtained by using more than one and/or more than one ice color coupling component which could not be obtained otherwise.

The textile material is printed orimpregnated with this mixture, and then treated with an acid, preferably a weak acid at elevated to hydrolyze the diazoimino compound and permit coupling to take place between the regenerated diazo salt and the ice color coupling component. Acetic and/or formic acids have been found to give very satisfactory results but the invention is not limited to these acids since hydrolysis of the diazoimino compound may be effected by numerous other acids or mixtures of acids, well known to one skilled in the art. The acid or acids used in treating the printed or impregnated diazoimino compound temperatures, 1;.

textile material may be in either the liquid or vapor phase.

It is to be understood that the ice color coupling component or components and the diazolmino compound or compounds need not be applied to the textile material simultaneously, but one may be applied prior to the other, the resulting reaction being fundamentally the same regardless of the order in which the reactants are applied.

' It is also to be understood that when reference is made to a mixture of an ice color coupling component and a diazoimino compound this mixture may contain various assistants such as starch, gum, alkali, and Turkey red oil. The compositions of these printing and dyeing mixtures are so well known that nodifliculty should beencountered in selecting the proper assistantsfcr any given purpose, in the event that assistants are required.

The process described in the present disclosure produces excellent dyeings and prlntings on textile material in a much more simplified manner than was previously possible. The colors produced are exceptionally uniform and fast, due in great part to the thorough impregnation of the fibers with the very soluble diazoimino compound. No deleterious side reactions take place to impair the efliciency of the process and the appearance and properties of the products produced. The secondary sugar amine, produced upon hydrolysis of the diazoimino compound, does not have a strong reducing effect, consequently, it does not reduce the diazo salt or interfere in any manner with the coupling of this diazo salt and the ice color coupling component. The compounds used are readily available at a very reasonable cost, and in addition the simplification of the printing or dyeing processes results in an appreciable saving to the manufacturer.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that we do not limit ourselves to the foregoing examples or description except as indicated in the following claims.

We claim;

1. A process for coloring material which comprises treating the material with a mixture comprising an ice color coupling component and a diazoimino compound, produced by coupling a secondary sugar amine with a diazotized aromatic amine containing no water-solubilizin'g group, then developing the color by subjecting the treated material to the action of a weak acid at elevated temperatures.

2. A process for coloring material which comprises treating the material with a mixture comprising an ice color coupling component and a diazoimino compound having the following general formula:

in which Aryl represents the residue of an aromatic amine containing no water-solubilizing group, and Z represents the residue of a secondary sugar amine, then developing the color-by subjecting the treated material to the action of a weak acid, preferably at elevated temperatures.

3. A process for coloring material-which comprises treating the material with a mixture comprising an ice color coupling component and, a,

diazoimino compound having the following gen eral formula:

in which Aryl represents the residue-of an and-- amine which may have non-water-solubilizing groups substituted thereon, R represents an alkyl, aralkyl, or completely'reduced carbocyclic radical, and x represents one of the integers 2, 3, 4, then developing the color by subjecting the treat-' ed material to the action of a weak acid, preferably at elevated temperatures.

4. A process for coloring material which comprises treating the material with a mixture cornprising an ice color coupling component and a diazoimino compound having the following general formula: I

. ongononnomon in which Aryl represents the residue of an I arylamine of the benzene, diphenyl, naphthalene, diphenylamine, azobenzene, anthraquinone or carbazole series, which may have non-water-solu bilizing groups substituted thereon, It represents an alkyl, aralkyl, or completely reduced carbocyclic radical, and :z: represents one of the integers 2, 3, 4, then developing the color by sub- ,iecting the treated material to the action of a weak acid, preferably at elevated temperatures.

5. A process for coloring material which comprises treating'tl'ie material with a mixture comprising an ice color coupling component selected from the group consisting of arylamides of 2-3- hydroxy-naphthoic acid, arylamides of hydroxycarbazoleor hydroxy-naphthocarbazole-carboxylic acids, arylamides of hydroxy-anthracenecarboxylic acids, alphaor beta-naphthol, ace-, toacetyl derivatives of arylamines, and phenylmethyl-pyrazolone, and a diazoimino compound having the following general formula: 1%

in which Arylrepresents the residue of an aryl- 12g amine of the benzene, diphenyl, naphthalene, diphenylamine, azobenzene, anthraquinone, or carbazole series, which may have non-water-solubilizing groups substituted thereon, R represents an alkyl, arallryl, or completely reduced carbocyclic radical, and :2: represents one of the integers 2, 3, 4, then developing the color by subjecting the treated material to the action of a weak acid at elevated temperatures.

6. A process for coloring material which comprises treating the materlal with a mixture comprising an ice color coupling component selected from the group consisting of arylamides of 2-3- hydroxy-naphthoic acid, arylamides of hydroxycarbazoleor hydroxy-naphthocarbazole-carboxylic acids, arylamides of hydroxy-anthracenecarboxylic acids, alphaor beta-naphthol, acetoacetyl derivatives of arylamines, and phenylmethyl-pyrazolone, and a diazoimino compound having the following general formula:

ongononpomon or completely reduced diphenyl, naphthalene, diphenylamlne, azobenzene, anthraquinone, or carbanole series, which contains no water-solubilizing group but which may have substituted thereon members selected from the group consisting of halogen, alkyl, zoylamino; R represents an alkyl, aralkyl, or completely reduced carbocyclic radical, and :e represents one of the integers 2, 3, 4, then developing the color by subjecting the treated material to the action of a weak acid at elevated temperatures.

7. A process for coloring material which com-s prises treating the material with a mixture comprising an arylamide of z-s-hydroxy-naphtholc acid having the following general formula:

CONE-R in which R represents the residue of an arylamine of the benzene or naphthalene series which may have non-water-solubillzing groups substituted thereon, and a diazoimino compound having the following general formula:

12 ar r-mm-m omwnonnomoa in which Aryl represents the residue of an arylamine of the benzene or naphthalene series which may have substituted'thereon non-watersolubilizing groups, R represents an alkyl, aralkyl, carbocyclic radical, and :n represents one of the integers 2, 3, 4, then developing the color by subjecting the treated material to the action of an acid selected from the group consisting of acetic and formic acid, at elevated temperatures.

8. A process for coloring material which comprises treating the material with a mixture comprising an arylamide of 2-3-hydroxy-naphthoic acid having the following general formula:

OH x zi \Y in which x and Y represent hydrogen, halogen,

alkyl or alkoxy groups, and a diazoimino compound having the following general formula:

is Aryl-N=N-N cmwnommmon in which Aryl represents the residue of an arylamlne of the benzene series, which may have substituted thereon members selected from the class consisting of halogen, alkyl, alkoxy, nitro and benzoyl-amino groups, R represents an alkyl group, and :2: represents one of the integers 2, 3, 4, then developing the color by subjecting the treated material to the action ofan acid selected from the group consisting of acetic and formic acid, at elevated temperatures.

9; A composition of matter which comprises an ice color coupling component and a diazoimino compound having the following general formula:

in which Aryl represents the residue of an aromatic amine containing no water-solubilizing group, and Z represents the residue of a secondary sugar amine.

10. A composition of matter which comprises an ice color coupling component and a diazoimino compoundhaving the following general formula:

CHKCHOHhCHaOH in which Aryl represents the residue of an arylamine of the benzene, dlphenyl, naphthalene, diphenylamine, azobenzene, anthraquinone or carbazole series, which may have non-water-solubilizing groups substituted thereon, R represents an alkyl, aralkyl, or completely reduced carbocyclic radical, and :1: represents one of the integers 2. 3, 4. 106

12. A composition of matter which comprises an ice color coupling component selected from the group consisting of arylamides of 2-3-hydroxy-naphthoic acid, arylamides of hydroxyor hydroxy-naphthocarbazole-carboxylic acids, arylamides of hydroxy-anthracenecarboxylic acids, alphaor beta-naphtha], acetoacetyl derivatives of arylamines, and phenylmethyl-pyrazolone; and a diazoimino compound having the following general formula:

in which Aryl represents the residue of an an]- amine of the benzene, diphenyl, naphthalene, diphenylamine, azobenzene, anthraquinone or carbazole series, which may have non-water-solubilizing groups substituted thereo R represents an alkyl, aralkyl, or completely reduced carbocyclic radical, and :2: represents one of the integers 2, 3, 4.

13. A composition of matter which comprises an ice color coupling component selected from the group consisting of arylamides of 2-3-hydroxy-naphthoic acid, arylamides of hydro carbazoleor hydroxy-naphthocarbazole-car- ArylN=NN 1 cmwnormomon in which Aryl represents the residue of an andamine of the benzene, diphenyl, naphthalene, di-

' ing group but which may have substituted there- I duced carbocyclic radical,- and'a: represents one of the integers 2, 3, 4. v r

14. A composition of matter which comprises an arylamide of z-3-hydroxy naphthoic acid having the following general formula:

ONE-R in which R represents the residue of an arylamine of the benzene ornaphthalene series which may have non-water-solubilizing groups substituted thereon, and a diazoimino compound having the following general formula:

Aryl-N=N-N om(cnon),cmorr in which Aryl represents the residue of an arylamine of the benzene or naphthalene series which may have substituted thereon non-watersolubilizing groups, R represents an alkyl, aralkyl,

or. completely reduced carbocyclic radical, and :1: represents one of the integers 2, 3, 4.

15. A composition of matter which comprises an arylamide of 2-3-hydroxy-naphthoic acid having the following general formula:

in which X and Y represent hydrogen, halogen, alkyl or alkoxy groups, and a diazoimino compound having the following general formula:

/R Aryl-N=NN ormononnomon in which X represents hydrogenor an alkyl or alkoxy group.

MILES AUGUSTINUS DAHLEN. FRITHJOF ZWILIGMEYER. 

